Anthracene dye and process of making same.



UNITED STATES PATENT OFFICE.

OSCAR BALLY, MANNHEIM, AND HUGO WOLFF, OF LUDWIGSHAFEN-ON-THE-RHINE, GER- MANY, ASSIGNORS TO BADISOHE ANILIN & SODA FABRIK, OF LUDWIGSHAFEN-ONTHE- RHINE, GERMANY, A CORPORATION.

mnnacsnn on: AND rnoczass or MAKING SAME.

Specification of'Letters Patent.

Patented Dec, 8, 1908.

Application filed June 13, 1907. Serial No. 378,876.

many, have invented new and useful Improvements in Anthracene Coloring-Matters, of which the following is a specification.

In the French Patent .No. 6719, 9th addition to No. 349,531, is disclosed the fact that compounds containing a benzanthrone group, such for instance as benzanthrone itself, and uinolin, and derivatives of halogenizing agent be converted into halogen derivatives WlllCh contain the halogen wholly or partly in the benzanthrone ring. The treatment of the benzanthrone compound with a halogenizing agent is fully described in the said French patent.

In the U. S. Patent No. 818,336, we have claimed the production of coloring matters by treating halogen benzanthrones with caustic alkali. .VVe have now discovered that on a plying this process to the specific halogen enzanthrones described -in the aforesaid French patent coloring matters are obtained which ossess properties different to those of the co' oring matters described and claimed in the said Patent No. 818,336.

The production of the coloring matter which we desire to be understood as claiming in the present specification can be carried out by heating the halogen benzanthrones described in the said French specification-with caustic alkali either alone, or in the presence of a diluting agent, or of a solvent. Instead of caustic alkalies themselves, their alcoholates can be employed. The halogenated. benzanthronecompounds used according to this invention differ from those described in Letters Patent No. 809,894 and used in the production 'of dyes accordin to Letters Patent N 0. 818,336," since the estuffs'obtainable by treatment with caustic alkali are different in the two cases, those of the present invention yielding dyestufis much more easily and the dyestuffs obtained roduce dyeings which are more lustrous and have redder shades than those described in the aforementioned specifications. Thesame difference also exists between the dyestufls produced according to the present invention and those obtainab e by treating benzanthrone coloring matters with halogenizing agents as described in thespecification of Letters Patent N o.- 837,775. The halo en benzanthrones obtainable by treating a enzanthrone compound with a halogenizing agent probably contain halogen in the benzanthrone ring and thus difier from the halogen benzanthrones obtained by condensing halogen anthracene compounds with glycerin. The production of coloring matters by heating a compound containing a benzanthrone grou is claimed generically in Letters Patent 0. 809,892 and we make no generic claim for the production of coloring matters from benzanthrones and for the coloring matters themselves; but

we wish to claim specifically the coloring matters obtain-able by treatingwith caustic alkali a halogen benzanthrone compound which can be obtained by treating a benzanthrone compound with a halogenizing agent. They are soluble. in' concentrated sulfuric acid giving green solutions and in nitroben:

zene giving reddish violet solutions. They dissolve in alkaline hydrosulfite yielding blue vats which dye vegetable fiber substantively giving red-violet to blue shades.

The following examples will serve to illustrate'further the nature of our inventionand the method of carrying it into practical effect, but our invention is not confined to these examples. The parts are by weight.

Example 1. Heat together twenty (20) parts of caustic potash and from twenty (20),

totwenty-five (25) parts of absolute alcohol until a thin fluid homogeneous melt is obtained and the temperature rises to one hundred and forty (140) de rees centi ade. Then add'five (5) parts of ch lorbenzant rone prepared as described inEXample 5 of the aforesaid French patent and heat for half an hour (30 minutes) -at-a temperature of one hundred and fifty 150) degrees centigrade. The chlorbenzanthrone dissolves at once with a blue color which gradually changes into red-violet. is complete, dissolve the melt in hot water When the reaction and complete the preci itation of the coloring matter by boilin t e solution, or more rapidly by passing air through the solution. Then filter and wash with hot water. The colorin from c orin, consists 'of a violet black matter so obtained, which is free paste and when dry of'a dark violet powder which is insoluble in water and dilute acids and alkalies. When purified it yields a green solution in concentrated sulfuric acid.

and the color does not chan e on the addition of boric acid. It is di 'cultly soluble in most organic solvents. It yields a redviolet solution with a brownish red fluorescence with nitrobenzener It dissolves in alkaline reducing agents yieldin a'blue vat which colors cotton blue and t ese shades upon washing turn into a beautiful reddish violet of excellent fastness.

Example 2. Introduce three (3) parts of monobrombenzanthrone, prepared according to Example 1 of the aforesaid French patent, into a solution of six (6) parts of' metallic sodium in fifty (50) parts of absolute alcohol, and heat in an oil bath for from three (3), to four (4), hours, at a tem erature of from one hundred and twenty 120), to

guished from "that obtainable to the said regoing exam le. Example 3. in the foregoing Example 2, the monobrombenzanthrone be replaced by dibrombenzanthrone of melting point two hundred and fifty-seven (257) degrees centigrade (obtainable as described in Example 4 of the aforesaid French patent), a coloring matter is obtained which, in the unpurified state, dissolves in concentrated sulfuric acid the solution being reddish brown. In the pure state, however, it yields a green solution in sulfuric acid and a reddish violet solution with -a brown-red fluorescence in nitrobenzene. yields, with alkaline reducing a ents, a blue vat which colors cotton blue s ades, these shades, on was {said upon drying in the air, ecoming. again Example 4'. If inthe foregoin Exam le 1, the chlorbenzanthrone be rep laced y a dibrombenzanthrone described in Example 4 of the aforesaid French patent, the coloring matter obtained is free from-bfomin and appears to be identical with that described in the said Example 1-. Exaniple 5. Mix five (5) parts of absolute It also contains bromin. It

, becomin reddish-violet,

alcohol withone hundred (100) parts of dry xylene, add gradually two- (2) parts. of metallic sodium and heat in a reflux apparatus in an oil-bath at a temperature of from one hundred and ten (110), to one hundred and twenty (120), degrees centigrade, taking care to prevent access of moisture or carbon dioxid to the apparatus. Hydro en is evolved and the sodium is gradually converted into sodium alcoholate which is suspended in the xylene, in a very finely divided gelatinous condition. When no more metallic sodium is resent, add ten (10) parts of chlorbenzant one (prepared as described in Example 5 of the aforesaid French patent) and boil the whole until the formation'of the coloring matter is complete. When the mass is cool, filter off the coloring matter and wash first with xylene, then with alcohol, and finally with water. The product obtained appears to be identical with that produced according to the foregoing Example 2.

Now what we claim is:

1. As new articles of manufacture the anthracene coloring matterswhich can be obtained by treating with caustic alkali a halogen benzanthrone compound obtainable by treating a benzanthrone compound with a halogenizing agent, which coloring matters dissolve in concentratedsulfuric acid, yielding reen solutions and in nitrobenzene yieldlng reddish violet solutions and in alkaline hydrosulfite yielding blue vats which dye vegetable fiber substantively giving red-violet to blue shades.

2. As anew article of manufacture the anthrac'ene colorin matter which can be obtained by treating with caustic alkali chlorbenzanthrone obtainable by treating benzanthrone with chlorin, which coloring matter yields a green solution in concentrated sulfuric acid, a reddish violet solution innitrobenzene and with alkaline hydrosulfite yields a blue vat which dyes vegetable fiber substantively giving red-violet shades.

In testimony whereof we have hereunto set our hands inthe presence of two subscribing witnesses.

I 7 OSCAR BALLY. HUGO WOLFF. Witnesses:

H. W. HARRIS, J. ALEG. LLOYD. 

